US5993629A - Regenerating of acids, particularly of strong organic acids, using bipolar membranes - Google Patents

Regenerating of acids, particularly of strong organic acids, using bipolar membranes Download PDF

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US5993629A
US5993629A US08/875,072 US87507297A US5993629A US 5993629 A US5993629 A US 5993629A US 87507297 A US87507297 A US 87507297A US 5993629 A US5993629 A US 5993629A
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membrane
anionic
compartment
bipolar
acid
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US08/875,072
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Claude Gavach
Christian Gancet
Alfred Mirassou
Frederic Perie
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Arkema France SA
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Elf Atochem SA
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Assigned to ELF ATOCHEM S.A. reassignment ELF ATOCHEM S.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GANCET, CHRISTIAN, GAVACH, CLAUDE, MIRASSOU, ALFRED, PERIE, FREDERIC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/42—Separation; Purification; Stabilisation; Use of additives
    • C07C303/44—Separation; Purification

Definitions

  • the present invention relates to the field of electrodialysis and the subject of the invention is more particularly the regeneration of strong organic acids by electrodialysis using bipolar membranes.
  • Acids and bases are important intermediates in the manufacture of a large number of chemicals. After they have been used, these acids and these bases generally are in the form of saline aqueous solutions from which it is necessary to strip them. For environmental and economic reasons, it is desirable to regenerate the initial acids and bases directly from the salts contained in these industrial effluents.
  • Electrodialysis using bipolar membranes enables such regeneration to be carried out.
  • This known method uses electrical energy to dissociate the water of the saline solution and to recover the acid and the base separately according to the reaction: ##STR1##
  • ion-exchange membranes and, more particularly bipolar membranes consisting of two faces, respectively selective to the anions and to the cations are used. Under the influence of an electric field, these membranes allow the following reaction:
  • H + +OH - ions are then recombined respectively with the anions X - and cations M + coming from the salt, and the species obtained are kept separate by conventional (monopolar) ion-exchange membranes in a three-compartment cell.
  • hydrochloric acid from NaCl [abstracts Chemical Abstracts 117(16): 153850m, 109(2): 11524u, 92(6): 43961f and 92(4): 25083s];
  • butyric acid from its sodium salt [abstract CA 116(18): 182124n];
  • bipolar membranes currently available on the market exhibit performance characteristics which vary depending on the technology used to manufacture them and depending on the supplier. Owing to their nature, bipolar membranes are in principle nonpermeable to cations and to anions which are respectively stopped by the anionic and cationic layers of the bipolar membrane.
  • the inventors have determined that the contamination of the acid with alkaline cation comes from the base compartment, which is separated from the acid compartment by the bipolar membrane, and not from the salt compartment, which is separated from the acid compartment by a monopolar anionic membrane.
  • the bipolar membranes used hitherto exhibit cation leakage, in particular sodium leakage, causing contamination of the acid during the regeneration operation.
  • the inventors have then found that the permeability of the bipolar membranes to cations, in particular sodium, may be considerably reduced, without a substantial contrary effect on the electrodialysis process, by adding an anionic membrane on the anionic face of the bipolar membranes.
  • the anion-exchange membranes have a very low transport number for cations and consequently constitute very effective barriers for limiting their diffusion.
  • the subject of the invention is therefore a method of regenerating acids, in particular strong organic acids, from their salts, by electrodialysis using a bipolar membrane, characterized in that at least one additional anionic membrane is applied against the anionic face, delimiting a base compartment, of the bipolar membrane so as to reduce the contamination of the acid compartment, lying on the other side of the bipolar membrane, with cations.
  • Sealing is provided around the entire perimeter between the anionic membrane and the bipolar membrane.
  • anionic membrane it is possible to use any commercial anionic membrane, for example those sold by Asahi Glass under the name SELEMION®, by Tokuyama Soda under the name NEOSEPTAE® or by Solvay. These commercial membranes generally have a thickness of between 0.1 and 1 mm and a pore diameter of between 1 and 30 ⁇ m.
  • the anion-exchange membranes are normally composed of a polymeric matrix, such as divinylbenzene-polystyrene, containing chemically bound cationic groups (for example ammonium or substituted ammonium), while the cationic-exchange membranes contain carboxylate or sulfonate groups.
  • the process according to the invention is aimed more particularly at the regeneration of methanesulfonic acid from its alkaline salts, in particular from the sodium salt, it may be applied generally to the regeneration of strong organic acids such as sulfonic acids and phosphonic acids, provided that their molecular mass is not too great.
  • the electrodialysis proper is carried out under the normal conditions known to those skilled in the art.
  • the invention also relates to an electrodialysis device, using a bipolar membrane for implementation of the process, consisting of a stack of cationic, bipolar and anionic membranes, with interposition of elements, between two clamping plates applied against electrode supports and characterized in that it includes, at each bipolar membrane, an additional anionic membrane applied against the anionic face of the bipolar membrane, this additional anionic membrane and the bipolar membrane being clamped in a sealed manner, around their entire perimeter, between two frame gaskets in such a way that no measurable space remains between the contacting faces of the additional anionic membrane and of the bipolar membrane.
  • all the elements of the stack including the bipolar membrane and the additional anionic membrane, have the same outer profiles and include, on their periphery, holes for fluid flow.
  • FIG. 1 is a diagram of an anionic membrane joined to a bipolar membrane, according to the invention, in which diagram the anionic membrane has been represented, for the purpose of explanation, away from the anionic face of the bipolar membrane, whereas in reality the anionic membrane is pressed against this anionic face.
  • FIG. 2 is a simplified diagram of electrodialysis cells of a known type.
  • FIG. 3 is a diagram, similar to that in FIG. 2, of electrodialysis cells according to the invention.
  • FIG. 4 is a simplified diagram, in perspective, of a bipolar membrane and an anionic membrane which are mounted, according to the invention, between two frame gaskets.
  • FIG. 5 is a section through a stack of compartments forming two cells.
  • FIG. 6 is a front view of a compartment separator.
  • FIG. 7 is a section on the line VII--VII in FIG. 6.
  • an anionic membrane A,10 (or simply 10) is joined to a bipolar membrane BP by being intimately applied against the anionic face of the bipolar membrane BP.
  • a gap has been shown between the anionic membrane A,10 and the anionic face of the bipolar membrane BP in order to show that the anionic membrane A,10 is an additional membrane which has been added.
  • the anionic membrane A,10 is applied intimately against the anionic face of the bipolar membrane BP and there is no fluid flow between these membranes parallel to their mid-plane, unlike what occurs in the various compartments of an electrodialysis cell.
  • the volume of the reservoir of each circuit was approximately 8 liters and the structure of the stack used, shown diagrammatically in FIG. 2 in which the symbols and letters have the following meanings:
  • a first treatment by electrodialysis of an MSA solution using a bipolar membrane was made using conventional electrodialysis cells illustrated in FIG. 2.
  • the acid compartment A is delimited, on one side, by the cationic face of a conventional bipolar membrane BP and, on the other side, by an anionic monopolar membrane.
  • the base compartment B On the other side of the bipolar membrane BP is the base compartment B which is therefore delimited by the anionic face of the bipolar membrane and by a cationic monopolar membrane.
  • the gaps between the membranes in a direction perpendicular to their mid-plane are sufficient to allow liquid to flow through the compartments in question.
  • the device according to the diagram in FIG. 2 was equipped with 4 WSI bipolar membranes supplied by WSI Technologies Inc., 5 cationic membranes (2 Nafion membranes from DuPont de Nemours and 3 CMV membranes from Asahi Glass) and 4 AAV anionic membranes from Asahi Glass.
  • the salt compartment was charged with 4 liters of a sodium mesylate solution to be regenerated (210 g/l and a pH of 3.0) and the acid and base compartments were charged respectively with 3 liters of a 0.56 N solution of MSA containing 150 ppm of Na + and 3 liters of a 0.53 N sodium hydroxide solution.
  • the flow rates were fixed at 90 1/h, the current at 10 A and the voltage adjusted between 16 and 20 V in order to obtain this current.
  • the concentration of the MSA solution had risen to 1.62 N for a final volume of 3.5 liters, and that of the NaOH solution to 2.16 N.
  • the sodium content in the MSA solution went from 150 to 1000 ppm, which corresponds to the diffusion of 3025 mg of sodium during the period of the test.
  • Example 2 Repeating the conditions in Example 1, an NaMS (sodium mesylate) solution was made to flow through the salt compartment S, while, instead of sodium hydroxide, a potassium hydroxide KOH solution was made to flow through the base compartment B.
  • NaMS sodium mesylate
  • KOH potassium hydroxide
  • the diffusion of the cations into the acid compartment A was monitored.
  • the respective concentrations in the MSA of the acid compartment A was 106 ppm in the case of Na + and 1 ppm in the case of K + .
  • the concentrations in the acid compartment A had become, respectively, 107 ppm in the case of Na + and 129 ppm in the case of K + .
  • the inventors conceived a way of enhancing the impermeability of the bipolar membrane BP to the cations by applying an additional anionic membrane against the anionic face of the bipolar membrane BP, as illustrated in FIG. 3.
  • FIG. 3 which is that of electrodialysis cells according to the invention, corresponds in its entirety to the conventional diagram in FIG. 2, the main difference being an additional anionic membrane 10 placed against the anionic face of each bipolar membrane BP.
  • Example 3 The same device was used as in Example 1, but by applying (FIG. 3) an AMV anionic membrane 10 from Asahi Glass on the anionic face of each of the 4 bipolar membranes.
  • the salt compartment was charged with 4 liters of a sodium mesylate solution (210 g/l at a pH of 2.9) and the acid and base compartments were charged respectively with 3 liters of a 0.7N MSA solution containing 73 ppm of Na + and 3 liters of a 0.5N NaOH solution.
  • the current observed was between 9 and 10 A.
  • the concentration of the MSA solution had risen to 1.75N for a final volume of 3.4 liters and that of the NaOH solution to 1.73N.
  • the sodium content in the MSA went from 73 to. 316 ppm, which corresponds to the diffusion of 852 mg of sodium.
  • Example 2 The same procedure as in Example 2 was carried out, but the AMV membranes used for reinforcing the anionic layer of the bipolar membranes were replaced by ADP anionic membranes from Solvay.
  • MSA and NaOH concentrations were, at the start, respectively 0.58N and 0.57N and, after operating for 5 hours at a voltage of 20 V, 1.46N and 1.62N, the observed average current being 6-8 A.
  • the final volume of MSA was 3.3 liters.
  • the sodium content of the MSA went from 56 to 123 ppm, which corresponds to the diffusion of 218 mg of sodium in 5 hours. This is approximately 4 times lower than in Example 2 and almost 14 times lower than in Example 1.
  • FIG. 4 shows diagrammatically the preparation of a bipolar membrane BP, the anionic face 11 of which is reinforced by an anionic membrane 10 according to the invention.
  • the additional anionic membrane 10 is applied against the anionic face 11, without leaving a measurable space between the two contacting faces.
  • the bipolar membrane BP and the associated additional anionic membrane 10, of rectangular shape in the example shown, are clamped, around their entire perimeter, between two frame gaskets 12 which are similar to those of the membranes and including a central opening 13, which is also rectangular.
  • This opening 13 exposes a major part of that face of the membrane 10 which lies on the opposite side to the bipolar membrane BP, and of the cationic face of this membrane BP.
  • the closed profile of the frame gaskets 12 includes several holes 14 for fluid flow, these being separated from each other. Stacking the holes in several elements makes it possible to create fluid-flow channels isolated from each other.
  • the bipolar membrane BP and the anionic monopolar membrane 10 have been shown with a profile having smaller dimensions than that of the frame gaskets 12, so that these membranes do not have fluid-flow holes similar to the holes 14.
  • the membranes BP and 10 may have external dimensions identical to those of the frame gaskets 12 and include holes similar to the holes 14 which are aligned with those in the frame gaskets 12 and those in the other elements of the stack.
  • This stack in FIG. 5 comprises, from right to left: a clamping plate 15; an electrode support 16; an electrode, namely an anode, 17 housed in the electrode support 16; a first frame gasket 12 applied against the electrode support 16; an electrode separator 18; again, a frame gasket 12; a cationic membrane 19; a frame gasket 12; a compartment separator 20B, corresponding to the base compartment; a frame gasket 12; the additional anionic membrane 10 applied against the anionic face of the bipolar membrane BP; a frame gasket 12; a compartment separator 20A corresponding to the acid compartment; a frame gasket 12; a monopolar anionic membrane 21; a frame gasket 12; a compartment separator 20S corresponding to the salt compartment; a frame gasket 12; and, again, a cationic membrane 19. Thereafter, the succession of elements indicated above is repeated, making it possible to form a base compartment followed by an acid compartment and a salt compartment.
  • An electrodialysis cell corresponds to the combination of the three salt, base and acid compartments.
  • an electrode support 22 in which the other electrode, namely the cathode 23, is housed.
  • Another clamping plate 15 is applied against the electrode support 22, on the side opposite the stack.
  • All the sheet-like elements of the stack all have an identical rectangular outer profile and include holes 14 distributed around their periphery, at the same places, in order to form flow channels.
  • the electrode support 16 and the electrode support 22 are provided with ducts such as 24, 25 suitable for communicating with a channel formed by a stack of holes 14.
  • the duct 24 constitutes the inlet for an acid to be regenerated in the example in question, while the duct 25 allows the regenerated acid to leave.
  • each compartment separator element for example the element 20A in the case of the acid compartment, is formed by a plate, of defined thickness, having at the center a rectangular opening 26 provided with a mesh 27 allowing diffusion of the liquid without preventing its flow.
  • the opening 26 is connected, for example along a segment of its edge, to a hole 14 via a hollowed part 28, having a trapezoidal profile, produced in the thickness of the sheet forming the element 20A.
  • This hollowed part 28 includes a membrane 29 having internal channels for the flow of the fluid.
  • Another region of the profile of the opening 26, for example its top right corner in FIG. 6, is connected, via another hollowed part 30 of the separator element 20A, to a hole 14 serving for discharge of the liquid.
  • the hollowed part 30 also includes a membrane 29 having internal channels for the flow of the liquid.
  • the length of the chamber along the direction of the axis of the stack is equal to the sum of two thicknesses of the frame gasket 12 and the thickness of the separator element 20A.
  • the inflow of the acid to be regenerated and its outflow can only take place via the multichannel membranes 29 lying in the hollowed regions 28 and 30 of the separator element 20A, between the frame gaskets 12.
  • the arrows drawn in FIG. 5 enable the flow of the acid to be followed.
  • the mounting of the additional anionic membrane 10, achieved by cladding, constitutes a simple and economical way of enhancing the barrier effect in respect of the cations at the bipolar membrane and of considerably reducing contamination of the regenerated acid by the cations.
  • any anionic (anion-exchange) membrane may be suitable for this enhancement of the barrier effect.
  • a membrane having a higher degree of crosslinking, such as ADP gives better results than a standard anionic membrane, such as AMV.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
US08/875,072 1995-01-18 1996-01-11 Regenerating of acids, particularly of strong organic acids, using bipolar membranes Expired - Fee Related US5993629A (en)

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Application Number Priority Date Filing Date Title
FR9500499A FR2729305A1 (fr) 1995-01-18 1995-01-18 Regeneration d'acides organiques forts par des membranes bipolaires
FR95/00499 1995-01-18
PCT/FR1996/000042 WO1996022154A2 (fr) 1995-01-18 1996-01-11 Regeneration d'acides, notamment d'acides organiques forts, par des membranes bipolaires

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JP (1) JPH10512804A (fr)
KR (1) KR19980701493A (fr)
CN (1) CN1169121A (fr)
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SG82649A1 (en) * 1998-10-29 2001-08-21 Degussa Process for treating aqueous solutions comprising bases and organic acids
US20110203929A1 (en) * 2008-11-17 2011-08-25 David Buckley Recovery of lithium from aqueous solutions
US11011756B2 (en) 2013-03-15 2021-05-18 Vanderbilt University Nanofiber-based bipolar membranes, fabricating methods and applications of same

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US6933381B2 (en) 2001-02-02 2005-08-23 Charles B. Mallon Method of preparing modified cellulose ether
US20070141456A1 (en) * 2005-12-21 2007-06-21 General Electric Company Bipolar membrane
CN102002725B (zh) * 2010-09-30 2012-04-04 杭州水处理技术研究开发中心有限公司 一种生产葡萄糖酸的双极膜装置
WO2017205458A1 (fr) * 2016-05-24 2017-11-30 Vanderbilt University Membranes bipolaires à base de nanofibres, procédés pour leur fabrication et applications correspondantes
CN102515317A (zh) * 2012-01-10 2012-06-27 刘景亮 用氨氮废水生产酸和氨水的方法及装置
CN102839383B (zh) * 2012-09-24 2015-03-18 山东东岳高分子材料有限公司 一种基于氯碱用全氟离子交换膜的有机酸盐电解制备有机酸的方法
CN104557621B (zh) * 2014-12-23 2017-12-22 浙江威拓精细化学工业有限公司 一种利用双极膜电渗析技术制备甲基磺酸的方法
CN109134317B (zh) * 2018-09-10 2021-11-12 合肥科佳高分子材料科技有限公司 一种双极膜电渗析制备l-10-樟脑磺酸的方法
US11998875B2 (en) 2021-12-22 2024-06-04 The Research Foundation for The State University of New York York System and method for electrochemical ocean alkalinity enhancement

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG82649A1 (en) * 1998-10-29 2001-08-21 Degussa Process for treating aqueous solutions comprising bases and organic acids
US6284116B1 (en) * 1998-10-29 2001-09-04 Degussa-Huels Aktiengesellschaft Process for treating aqueous solutions comprising bases and organic acids
US20110203929A1 (en) * 2008-11-17 2011-08-25 David Buckley Recovery of lithium from aqueous solutions
US11011756B2 (en) 2013-03-15 2021-05-18 Vanderbilt University Nanofiber-based bipolar membranes, fabricating methods and applications of same

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DK0804277T3 (da) 1999-08-02
ATE173414T1 (de) 1998-12-15
KR19980701493A (ko) 1998-05-15
JPH10512804A (ja) 1998-12-08
WO1996022154A2 (fr) 1996-07-25
CN1169121A (zh) 1997-12-31
TW335390B (en) 1998-07-01
FR2729305A1 (fr) 1996-07-19
FR2729305B1 (fr) 1997-02-28
ES2125709T3 (es) 1999-03-01
DE69600994T2 (de) 1999-07-01
WO1996022154A3 (fr) 1996-10-10
EP0804277B1 (fr) 1998-11-18
EP0804277A2 (fr) 1997-11-05
DE69600994D1 (de) 1998-12-24

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